490513 5280pif.doc/008 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（/ ) 本發明是有關於一種包含少量添加物之聚酯纖維和/ 或纖絲，與其製造方法。 眾所皆知，包含少量添加物之聚酯纖維和/或纖絲， 依照其混合物的成分，來進行熔融紡絲（melt spinning)。 通常，在相同的紡絲速度下進行時，可增加未拉伸紗 (undrawn yarn)之斷裂伸長量（elongation at break) 〇 歐洲專利第〇,〇47,464 B1號曾教導聚甲基丙烯酸甲 酯（polymethyl methacrylate)(下文中簡寫爲PMMA)主要可 用來增加較高紡絲速度下之斷裂伸長量。 此份文件描述混合於熔融狀態之未成團狀物質之使 用，其未成團狀物質包含了聚甲基丙烯酸甲酯添加物之聚 酯。此步驟爲達到均質(homogenous)產物之最佳化的預混 合步驟。然而，如同歐洲專利第〇,〇47,464 Β1號所揭露的， 當高分子量的PMMA做爲添加物時，在紡絲程序上便出 現了問題(見第5頁第11至13行）。 歐洲專利第〇,631，638 B1號，如同歐洲專利第 0,047,464 B1號，也曾描述聚甲基丙烯酸甲酯具有有限的 紡絲容量（capacity)。歐洲專利第0,631，638 B1號描述包含 0.1-5 wt%的纖維聚合物，其相對於纖維聚合物具有50-90% 之硫亞氨化聚甲基丙烯酸烷基酯，基本上是以包體 (inclusion)的形式存在。然而，硫亞氨化聚甲基丙烯酸烷 基酯添加物其很大的缺點爲添加物具有很高的價位。硫亞 氨化聚甲基丙烯酸烷基酯添加物的花費顯示所需的添加物 的製程並不經濟。再者，所需的添加物並不能大量製造， 4 ---------------裝—— (請先閱讀背面之注音？事項me寫本頁) 訂· -線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 490513 A7 5280pif.doc/008 oy 五、發明說明（7) 且目前僅有少數的工廠製造。如上所述，另一缺點爲其受 限於紡絲安全。當此種物質作爲添加物時，將會更常發生 纖維斷裂。 歐洲專利第0,047,464B1號揭露聚甲基丙烯酸甲酯的 最大分子量爲16,000克/莫耳（見第9頁表格5)。而且，歐 洲專利第〇,〇47,464Β1號曾提及PMMA直徑在聚酯介質中 超過Ιμιη，如此增量使得斷裂伸長量不再是最佳化。否則， 則不再進一步討論此包體的構形。 如同歐洲專利第〇,〇47,464Β1號與於1998年格陵維 耳(Greenville)”HP5最高經濟聚酯ρογ製程纖維製造會議” 中所述，例如在未順向（unoriented)聚酯紗球中出現了無法 接受的包體，亦即，由紡絲機以球狀或滴狀的形式押出之 未順向熔融纖維。歐洲專利第0,047,464B1號中第4頁第 13至15行與第5頁第8行和第9行曾揭露包體(類似球形 培林）在纖維的方向可能導致”滾動效應（rolling effect)”， 這將導致聚酯的延遲變形。 然而，在未順向聚酯紗球中，添加物包體之種類形 式、尺寸與所需的最終產品之種類性質，及實質上對產業 有用的重要紡絲行爲有關，上述結果並未被證實。 因此，本發明的目的就是在提供一種使聚合混合物 具可利用性之聚酯纖維與纖絲之製造，其包含不超過4% 的添加物，且可好好進行紡絲，使得其製造方法因少量的 添加物而使添加物具有大的可利用性，又由於斷裂伸長量 的大幅增加，而具有較高的經濟價値。 5 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公釐） ---------------裝 i — (請先閱讀背面之注意事寫本頁) ¾. 490513 A7 5280pif.doc/008 B7 五、發明說明（θ ) 可藉由本發明之纖維與/或纖絲及其製造方法，達成 上述之目的。 本發明是提供一種纖維與纖絲，主要包含聚對苯二 甲酸乙二醇酯以作爲纖維-形成聚合物，其特徵在於纖維 與纖絲包含相對於纖維-形成聚合物0的聚甲基丙 烯酸甲酯，聚甲基丙烯酸甲酯之平均分子量約介於20,000 與200,000克/莫耳間，主要是似桿狀包體的形式，其是在 由紡絲機押出之尙未順向熔融紡絲狀態下進行測量，藉以 使得聚甲基丙烯酸甲酯之似桿狀包體之側向粒子尺寸小於 800nm，且使得製造纖維與纖絲時，其紡絲纖維的紡絲速 度高達8000公尺/分。 此外，本發明提供一種製造熔融紡絲纖維或纖絲的 方法，該熔融紡絲纖維或纖絲包括聚對苯二甲酸乙二醇酯 作爲纖維-形成聚合物，其先經由縮合聚合或熔融之纖維-形成聚合物的熔融步驟後，進行熔融紡絲，該方法包括於 進行熔融紡絲與分散未順向熔融纖維之纖維-形成聚合物 中之第二聚合物前，先混合纖維-形成聚合物與相對於纖 維-形成聚合物〇.l-4wt%之第二聚合物，其實質上包括具 有約介於20,000與200,000克/莫耳間之平均分子量的聚 甲基丙烯酸甲酯，進行熔融紡絲過程中，纖維之紡絲速度 設定高達8000公尺/分，經由押出機押出之未順向纖維包 體，而得到具有側向粒子尺寸小於800nm之似桿狀第二聚 合物包體。 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------裝--- (請先閱讀背面之注意事寫本頁) 訂· -·線- 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 490513 A7 5280pif.doc/008 R7 五、發明說明（4 ) 圖式之簡單說明 第1圖、第2圖與第3圖繪示依照本發明，一種介 質聚合物(PET)之熔融纖維之REM的剖面影像圖。 較佳實施例 令人訝異的，我們發現可由聚酯之聚合混合物製造 的纖維與纖絲，特別是聚對苯二甲酸乙二醇酯(polyethylene terephthalate; PET)與含少量添加物的聚甲基丙烯酸甲酯， 即使在高的紡絲速度下，也能夠同時表現出非常高的斷裂 伸長量，與突出的紡絲行爲。我們淸楚地瞭解聚酯之混合 物，例如PET與聚甲基丙烯酸甲酯的混合物，與聚甲基丙 烯酸甲酯對增加斷裂伸長量的影響，亦知道此種混合物紡 絲時纖維斷裂的趨勢。此種纖維斷裂傾向於當使用具有很 高分子量的聚甲基丙烯酸甲酯時發生。 如此，如同上述，歐洲專利第〇,〇47,464 B1號曾描 述，雖然聚甲基丙烯酸甲酯分子量的增加致使斷裂伸長量 增加的影響增加，也會同時出現紡絲上的問題。換句話說， 如同習知技藝所教導的，由於增長之纖維斷裂的趨勢，高 分子量的聚甲基丙烯酸甲酯，其使伸長量增加的加強效應 可能無法被接受。如此，基於歐洲專利第〇,〇47,464 B1號 所述之製造方法，其經濟可行性便因此受限。 而令人訝異的是，我們發現本發明利用添加物分散 尙未順向（still-unoriented)之聚酯紗球’並不會像歐洲專利 第 0,047,464 B1 號與於 1998 年格陵維耳(GreenVille)，，HP5 最高經濟聚酯POY製程纖維製造會議”中所述，具有似滴 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------------裝 i I (請先閱讀背面之注意事寫本頁) 訂· •線. 490513 5280pif.doc/008 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（g ) 狀或似球狀產生，而是如同第1圖、第2圖與第3圖中所 顯示的，生成新的、具有似桿狀或似蟲狀等拉伸的形狀° 因此，本發明之實施例中描述具有新的特徵結構之PMMA 包體，特別是在非常高的PMMA分子量下，且可改善紡 絲的容量。 在此需注意的是，新的桿狀結構之側向直徑非常地 小。在實施例中，似桿狀包體例如具有約300-400nm之側 向直徑，其是測量由紡絲機押出之尙未順向的熔融纖維， 即所謂的紗球(yarn ball)。 重要的是，直徑可小於800nm。較佳是小於600 nm， 最好是小於400 nm。 然而，本發明之具尙未順向聚酯介質的似桿狀結構 之聚甲基丙烯酸甲酯包體，與歐洲專利第0,047,464 B1號 中所觀察的並不相同。似桿狀的結構通常必須遵守不同於 歐洲專利第〇,〇47,464 B1號中所述之機制。且在本文中， 其很有可能爲最佳祐絲行爲的理由。 如此，聚合物介質中具有似滴狀或似球狀的包體可 降低位向的影響，也由於聚酯介質所期望的分子運動垂直 於纖維拉伸的方向，因此紡絲製程可能具有較多或較少的 分散性。 以本發明第一次發現之似桿狀包體的情況來說，應 減少橫跨纖維之聚酯分子的分散成分，此爲紡絲行爲改進 的原因。 本發明包括PMMA的聚合混合物，於高紡絲速度下 8 --------------裝—— (請先閱讀背面之注意事寫本頁) 訂· 線！ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 490513 A7 5280pif.doc/008 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（& ) 紡絲並不會發生例如使用習知空氣橫向流動的擴散問題。 然而，另一熟知且合適的冷卻設備，例如藉由空氣 對快速紡絲的纖維或排列在纖維束中心的空氣擴散體施加 吸力，而用來被動冷卻的設備。 通常，本發明適用於製造部分順向紗（partially oriented yarn; POY)(如同實施例中所解釋的）與纖維產品 (例如短纖(staple fiber))。而業者也熱烈地討論於非常低速 的紡絲速度下進行的情形（Ullmann’s Encyclopedia of Industrial Chemistry，5th Ed.，Vol.AlO，Fibers，3 General Production Technology，pp.550-561)。本發明揭露了 除了相 對應高產能的熔融紡絲之外，且特別是在纖維發展的情 形，與在纖維生產線上重大拉伸的情形下，合乎經濟效益 之粒子。 本發明之纖維製造方法，較佳係選擇範圍介於800-2400公尺/分的紡絲速度，雖然本發明並不限制紡絲速度， 但製造部分順向纖絲紗（POY)時，較佳使用3000-8000公 尺/分的紡絲速度。 作爲添加劑之具有商業可利用性的聚甲基丙烯酸甲 酯產品（DEGALAN® of DEGUSSA Co.)之優點已經證實。 儘管高分子量的DEGALAN®型G8E的分子量約爲126,580 克/莫耳（以下列所描述之方法所量測的平均分子量），其結 果發現非常地適合作爲添加物。除嚴重的伸長量增加外， 具有非常高分子量的物質會使具有聚酯的混合物，於高紡 絲速度下造成很大的容量。由於包含非常高分子量 9 (請先閱讀背面之注意事 寫本頁) --裝 線！ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 490513 5280pif.doc/008 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（1) DEGALAN®型G8E與聚對苯二甲酸乙二醇酯(pet)的混合 物具有優越的紡絲行爲，因此可假設低分子量（例如 20,000-120,000克/莫耳）的PMMA型態，可改善習知的紡 紗f了爲。 再者，比較歐洲專利第0,631，638 B1號所述之添加 物成分（硫亞氨化聚甲基丙烯酸酯），聚甲基丙烯酸甲酯是 比較便宜及具有較佳的可利用性。 根據拉伸量增加的影響，本發明之聚甲基丙烯酸甲 酯以介於20,000與200,000克/莫耳間的分子量（平均重量) 較爲適合。較佳的分子量係介於50,〇〇〇與160,000克/莫 耳間，而最好是介於80,000與140,〇〇〇克/莫耳間。 以下列測量方法（internal analysis direction No. LCO12 of EMS CHEMIE AG)測量之PMMA分子量的値爲： PMMA之分子量與重量平均莫耳質量（Mw)的分佈係 以凝膠透析色譜法（GPC)決定。亦即，具有液相層析之基 本成分泵裝置、層析管柱與偵測器的GPC測量裝置。此 測量方法使用具有IR偵測器之Waters Co. type GPC 150A 的裝置來進行。250mm x 7mm(直徑）之第四獨立管柱與一 連串形成lm總管柱長度之其中之一連接。這些管柱以 ΙΟμπι 的 MERCK LiChrogel®，並結合 PS4000、PS400、PS20 與PS4(係指孔隙尺寸）來塡滿四個獨立的部分，以使PMMA 分子量的每個部分（fraction)可以選擇性地分離。氯仿可作 爲PMMA樣品的儲存溶液，並以0.1%的1，2-二氯苯作爲 浮標。以流速lml/min的氯仿作爲洗提劑(eluent)。爲了製 10 (請先閱讀背面之注意事 寫本頁) 裝 ;線- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 490513 A7 5280pif.d〇c/〇〇8 ηγ 五、發明說明（2 ) 備樣品，將每個50mg之PMMA樣品置於20mL密封的玻 璃容器中，之後以具有標記的儲存溶液來塡滿，並攪拌至 完全溶解。首先，需以相同方式製備至少5個標準單位的 PMMA，其係使用 POLYMER LABORATORIES Co·來量測 分子量，而此分子量範圍爲5,720<MW<360,000。分子量的 測量係以標準値來計算。每個玻璃容器以200μ1的樣品溶 液來注射。所有處理皆於下進行。根據本方法之窄 標準，測量値（凝膠透析色譜）的判斷係使用GPC軟體， MILLENIUM(by WATERS)來判斷。 相對於作爲纖維-形成聚合物的聚酯，混合的PMMA 的量的範圍爲0.1-4%。較佳範圍係在〇·2至3%間，最好 是在〇·3至2%間的PMMA的量。 作爲PET添加物的聚甲基丙烯酸甲酯，例如可以使 用所謂的連續改質（continuous modification)的聚合物熔融 (DE 40 39 857 C2)之溶融處理法(meit conditioning)，加以 混合。在此DE 4〇 39 857 C2的內容係作爲參考。由縮合 聚合或重新熔融之部分熔融量，是由主要熔融主流分出 來。此部分支流進入旁流押出機，之後以粒狀、粉末狀的 形式混合，較佳是以珍珠狀的形式混合，之後再分散。使 分散與混合的熔融濃縮物直接返回主要熔融線，之後稀釋 至最終的濃度。 除了上述的熔融處理法外，例如可以藉由熔融押出 機產生純的添加熔融量的方式，將其注入主要熔融流中。 然後，於纖維-形成介質聚合物(例如聚對苯二甲酸乙二醇 本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公楚) --------------裝—— (請先閱讀背面之注意事寫本頁) -線- 490513 A7 5280pif.doc/008 07 經濟部智慧財產局員工消費合作社印製 五、發明說明（q ) 酯）中，對一均質與添加物包體提供一相對排列混合成分。 若使用PET團狀物作爲起始物，且熔融於紡絲押出 機中，可以直接量測在紡絲押出機中做爲PET團狀物的添 加物（以粒狀、粉末狀或珍珠狀的形式）之PMMA。添加物 分散在聚對苯二甲酸乙二醇酯中，之後進行熔融混合物的 紡絲。由於熔融處理法有利於熔融PET量的細微分佈，因 此在此混合的各種形式中，較佳爲珍珠狀PMMA起始的 形式。此外，商業化PMMA的產品通常較容易以這個形 式取得。此種珍珠狀形式可想像爲具有直徑約0.3mm的小 球，有時亦稱細粒(grit)。 添加物可同時作爲純的基質及以主要混合成分的形 式。此外，其餘添加的基質或添加物亦能夠同時被檮碎與 紡絲。聚對苯二甲酸乙二醇酯本身包含例如去光劑（二氧 化鈦）、安定劑與觸媒等一般的添加劑。本申請案之聚對 苯二甲酸乙二醇酯（PET)或聚酯爲包含至少80%聚對苯二 甲酸乙二醇酯單元的聚酯，與來自除了乙二醇的二元醇之 最大20%單元，例如二甘醇、1，4-丁二醇、或除了對苯二 甲酸的二羧酸，例如，間苯二甲酸、六氫化對苯二甲酸與 二苯酸。 聚對苯二甲酸乙二醇酯能夠以具有3-4官能機醇或酸 基之接枝劑（branching agent)的少莫耳量，選擇性地來進 行改質，例如三甲基丙院、trimethyloletane、pentaerythrite、 甘油、trimesic acid、偏苯三酸或均苯四甲酸。 然而，爲了對染色能力進行改質，起始聚酯可包含 (請先閱讀背面之注意事 裝—— 寫本頁) •線！ Φ 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） 490513 5280pif.doc/〇〇8 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（~) E 知的添 口物，例如 sodium-3,5-dicarboxybenzol sulfonate 〇 在熔融線上，例如可使用其他動態與/或靜態攪拌機。 因此，動態與/或靜態攪拌機可直接置放在紡絲組件之前。 本發明之實施例中，首先，將可以任何一種混合變 體製造之待用（ready-to-use)、分散的熔融混合物，紡絲成 團狀物，而不紡絲成纖維。具有高成效的團狀物，可利用 習知具有熔融押出機之紡絲機器，進行後續處理，並紡絲 成纖維或纖絲。此製程中，二級加工廠商，例如團狀物製 造商的顧客，利用本發明之聚酯改質，不需提供習知具有 昂貴測量及混合設備之紡絲機器，且不需額外購買分離的 添加劑。如此，對二級加工廠商來說，所有的處理如同一 般的PET團狀物一樣簡單。 第1、2與3圖顯示依據本發明介質聚合物(PET)之熔 融紡絲的REM橫切面影像，此爲未順向狀態下的晶片面。 尤其是，第3圖（桿狀，側向橫切)繪示PMMA添加物（指 纖維軸）之軸狀包體。 本發明以下列的實施例作詳細的說明，此實施例並 不限制本發明。 習知的紡絲機器，例如是使用Ullmann’s Encyclopedia of Industrial Chemistry，5th Ed.，Vol.AlO，Fibers，3 General Production Technology，pp.550-561 中所述之機器。 實施例 利用6種纖維製造紡絲裝置測試的結果列於表1。表 (請先閱讀背面之注意事項Hi寫本頁) --裝 訂 --線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 490513 5280pif.doc/008 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明够明（丨（） 1顯示於捲取速度（Vwick)爲4,950公尺/分下紡絲測試的結 果。紡絲的溫度範圍爲208-295°C，較佳爲285QC。冷卻的 纖絲需使用被動的冷卻方法，例如DE197 16 394 C1。在 冷卻線紡絲步驟進行之後，紗球被導向低溫的羅拉（godet-duo)，之後才進行捲取。羅拉的速度爲5000公尺/分，亦 即除了空白樣品”Blank-2”之外的各變體啓動紡絲的速度。 物種”Blank-2”(習知，不需要添加劑）之羅拉速度爲3225 公尺/分。混合進入的添加劑使用熔融處理法(DE 40 39 857 C2)，其通常應用於連接於紡絲機器之習知連續聚對苯二 甲酸乙二醇酯縮合聚合的熔融改質。爲了製造紗球，常使 用織布用的EMS-CHEMIE AG聚對苯二甲酸乙二醇酯，亦 可稱爲GRILENE®M764。所使用的添加物爲DEGUSSA Co. 的聚甲基丙烯酸甲酯，亦可稱爲DEGALAN⑧G8E，其分 子量（平均重量）爲126,580克/莫耳。濃度爲0.65-(K90wt%。 聚甲基丙烯酸甲酯包體的平均側向直徑小於400nm(見第 1、2、3 圖）。 紡絲行爲佳。僅製造整個絲餅（spool)。 表格2顯示締鬈紗(textured yarn)的紡織資料。改質 的聚酯所達成的品質資料與好的、以習知技藝製造的締鬈 紗相一致。然而，當僅有一般的POY紗在約3200公尺/分 的紡絲速度下紡絲，其紡絲機器之生產率分佈非常之大。 (請先閱讀背面之注意. 事項»寫 本頁)490513 5280pif.doc / 008 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (/) The present invention relates to a polyester fiber and / or filament containing a small amount of additives, and a method for manufacturing the same. It is known that polyester fibers and / or filaments containing a small amount of additives are melt-spun according to the composition of the mixture. Generally, at the same spinning speed, the elongation at break of undrawn yarn can be increased. European Patent No. 0, 〇47,464 B1 has taught polymethyl methacrylate ( Polymethyl methacrylate (hereinafter abbreviated as PMMA) is mainly used to increase the elongation at break at higher spinning speeds. This document describes the use of non-agglomerated substances mixed in a molten state, the non-agglomerated substances comprising polyesters of polymethyl methacrylate additives. This step is an optimized premixing step to achieve homogenous products. However, as disclosed in European Patent No. 0,047,464 B1, when high molecular weight PMMA is used as an additive, problems occur in the spinning process (see lines 5 to 11 on page 5). European Patent No. 0,631,638 B1, like European Patent No. 0,047,464 B1, has also described that polymethyl methacrylate has a limited spinning capacity. European Patent No. 0,631,638 B1 describes a fiber polymer containing 0.1-5 wt%, which has 50-90% thioimidized polyalkyl methacrylate relative to the fiber polymer, and is basically an inclusion (inclusion). However, the thioimidized polyalkylmethacrylate additive has a great disadvantage in that the additive has a high price point. The cost of the thioimidized polyalkyl methacrylate additive shows that the required additive manufacturing process is not economical. In addition, the required additives cannot be manufactured in large quantities. 4 --------------- Pack-(Please read the phonetic on the back? Matters write this page) Order · -line · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 490513 A7 5280pif.doc / 008 oy 5. Description of invention (7) Manufacturing. As mentioned above, another disadvantage is that it is limited to spinning safety. When this substance is used as an additive, fiber breakage will occur more often. European Patent No. 0,047,464 B1 discloses that the maximum molecular weight of polymethyl methacrylate is 16,000 g / mole (see Table 5 on page 9). Furthermore, European Patent No. 0,047,464B1 mentioned that the diameter of PMMA exceeds 1 μm in the polyester medium, such an increase makes the elongation at break no longer optimized. Otherwise, the configuration of this inclusion will not be discussed further. As described in European Patent No. 0,047,464B1 and the Greenville 1998 HP5 Highest Economic Polyester Process Fiber Manufacturing Conference, for example in unoriented polyester yarn balls Unacceptable inclusions appeared, that is, non-directionally fused fibers extruded in a ball or drop form by a spinning machine. In European Patent No. 0,047,464B1, lines 4 to 13 on pages 4 and lines 8 and 9 on page 5 have disclosed that inclusions (similar to spherical bearings) in the fiber direction may cause a "rolling effect" This will cause delayed deformation of the polyester. However, in the non-directional polyester yarn ball, the type and size of the inclusions are related to the type and nature of the final product required, and the important spinning behavior that is practically useful to the industry. The above results have not been confirmed. . Therefore, the object of the present invention is to provide a polyester fiber and a filament that make the polymerizable mixture usable, which contains no more than 4% of additives, and can be well-spun, so that the manufacturing method is limited by a small amount. Additives make the additives have a large availability, and because of the large increase in elongation at break, it has a higher economic value. 5 This paper size is in accordance with Chinese National Standard (CNS) A4 (21〇x 297mm) --------------- Installing i — (Please read the notes on the back first to write this page ) ¾. 490513 A7 5280pif.doc / 008 B7 V. Description of the invention (θ) The above-mentioned object can be achieved by the fiber and / or filament of the present invention and its manufacturing method. The present invention provides a fiber and a fibril, which mainly include polyethylene terephthalate as a fiber-forming polymer, and is characterized in that the fiber and the fibril include polymethacrylic acid relative to the fiber-forming polymer 0 Methyl esters, polymethyl methacrylates have an average molecular weight between about 20,000 and 200,000 g / mole, mainly in the form of rod-like inclusions, which are not melt-spun in the forward direction of the extruder extruded by the spinning machine. The measurement is performed under the condition that the lateral particle size of the rod-like inclusion body of polymethyl methacrylate is less than 800 nm, and the spinning speed of the spinning fiber is as high as 8000 m / min when manufacturing fibers and filaments. . In addition, the present invention provides a method for manufacturing a melt-spun fiber or filament comprising polyethylene terephthalate as a fiber-forming polymer, which is first polymerized or melted by condensation. After the fiber-polymer-forming melting step, melt-spinning is performed. The method includes mixing the fiber-forming polymer before performing the melt-spinning and dispersing the second polymer in the fiber-forming polymer that disperses the non-directionally fused fibers And a second polymer at 0.1-4 wt% relative to the fiber-forming polymer, which essentially comprises polymethyl methacrylate having an average molecular weight between about 20,000 and 200,000 g / mol During the spinning process, the spinning speed of the fiber is set as high as 8000 m / min, and the non-directional fiber inclusions extruded through the extruder to obtain a rod-like second polymer inclusion having a lateral particle size of less than 800 nm. 6 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -------------- Loading --- (Please read the notes on the back first to write this page) Order ·-· Line-Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 490513 A7 5280pif.doc / 008 R7 V. Description of the invention (4) Brief description of the drawings Figure 1, Figures 2 and 3 show cross-sectional image views of REM of a fused fiber of a dielectric polymer (PET) according to the present invention. The preferred embodiment is surprising, and we have found that fibers and filaments that can be made from polymer blends of polyesters, especially polyethylene terephthalate (PET) and polymethacrylate with small amounts of additives Methyl acrylate, even at high spinning speeds, can simultaneously exhibit a very high elongation at break and outstanding spinning behavior. We thoroughly understand the effects of polyester blends, such as the blend of PET with polymethyl methacrylate, and polymethyl methacrylate, on the increase in elongation at break. We also know the tendency of fibers to break when such blends are spun. Such fiber breaks tend to occur when polymethyl methacrylate having a very high molecular weight is used. Thus, as mentioned above, European Patent No. 0,047,464 B1 described that although the increase in the molecular weight of polymethyl methacrylate causes the effect of the increase in elongation at break to increase, problems in spinning also occur at the same time. In other words, as taught in the conventional art, due to the tendency of growing fibers to break, the strengthening effect of high molecular weight polymethyl methacrylate, which increases the amount of elongation, may be unacceptable. Thus, based on the manufacturing method described in European Patent No. 〇47,464 B1, its economic feasibility is therefore limited. Surprisingly, we found that the present invention uses additives to disperse still-unoriented polyester yarn balls, which does not look like European Patent No. 0,047,464 B1 and Greenwich (1998) GreenVille), as described in the HP5 Highest Economic Polyester POY Process Fiber Manufacturing Conference, has paper-like paper standards that apply Chinese National Standard (CNS) A4 specifications (210 X 297 mm) --------- ------ Install i I (please read the note on the back to write this page) Order · • Line. 490513 5280pif.doc / 008 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ) Shape or spheroidal shape, but as shown in Figure 1, Figure 2 and Figure 3, a new shape with a rod-like or insect-like shape is stretched. Therefore, the present invention PMMA inclusions with new characteristic structures are described in the examples, especially at very high PMMA molecular weights, which can improve spinning capacity. It should be noted here that the lateral diameter of the new rod-like structure is very In the embodiment, the rod-like inclusions have, for example, a lateral diameter of about 300-400 nm, which is Measure the non-directionally fused fibers extruded by the spinning machine, so-called yarn balls. Importantly, the diameter can be less than 800 nm. It is preferably less than 600 nm, and most preferably less than 400 nm. However, The polymethyl methacrylate inclusions of the present invention having a rod-like structure with non-directional polyester media are not the same as those observed in European Patent No. 0,047,464 B1. The rod-like structure must generally observe different The mechanism described in European Patent No. 〇47,464 B1. And in this paper, it is likely to be the reason for the best Yossi behavior. Thus, the polymer medium has a drop-like or spherical-like bag The body can reduce the effect of orientation, and because the desired molecular motion of the polyester medium is perpendicular to the direction of fiber stretching, the spinning process may have more or less dispersion. It is similar to the first discovery of the present invention. In the case of rod-shaped inclusions, the dispersion of polyester molecules across the fiber should be reduced, which is why the spinning behavior is improved. The present invention includes a polymerized mixture of PMMA at high spinning speeds 8 ---- ---------- install-(please first Read the note on the back and write this page) Order and line! This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 490513 A7 5280pif.doc / 008 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (&) Spinning does not occur, for example, with the diffusion of conventional air flowing laterally. However, another well-known and suitable cooling device, such as fast spinning fibers or arrays of fibers by air The air diffuser in the center of the beam applies suction and is used for passive cooling equipment. Generally, the present invention is applicable to the manufacture of partially oriented yarns (POY) (as explained in the examples) and fiber products (such as staple fibers). The industry also discussed the situation at a very low spinning speed (Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. AlO, Fibers, 3 General Production Technology, pp.550-561). The present invention discloses particles that are economically efficient, in addition to the corresponding high-capacity melt-spinning, and especially in the case of fiber development, and in the case of significant stretching on the fiber production line. The fiber manufacturing method of the present invention preferably selects a spinning speed in the range of 800-2400 m / min. Although the spinning speed is not limited by the present invention, when manufacturing partly forward filament yarn (POY), It is best to use a spinning speed of 3000-8000 m / min. The advantages of commercially available polymethyl methacrylate products (DEGALAN® of DEGUSSA Co.) as additives have been proven. Although the high molecular weight DEGALAN® type G8E has a molecular weight of about 126,580 g / mole (average molecular weight measured by the method described below), the results have found it to be very suitable as an additive. In addition to the severe increase in elongation, substances with very high molecular weights can cause mixtures with polyesters to create a large capacity at high spinning speeds. Because it contains a very high molecular weight 9 (please read the note on the back first to write this page)-wiring! This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 490513 5280pif.doc / 008 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) DEGALAN® G8E and poly The blend of ethylene terephthalate (pet) has superior spinning behavior, so it can be assumed that the PMMA type of low molecular weight (such as 20,000-120,000 g / mole) can improve the conventional spinning f . Furthermore, compared with the additive component (thioimidized polymethacrylate) described in European Patent No. 0,631,638 B1, polymethylmethacrylate is relatively cheap and has better availability. Based on the effect of the increase in the amount of stretch, the polymethyl methacrylate of the present invention is suitably a molecular weight (average weight) between 20,000 and 200,000 g / mole. The preferred molecular weight is between 50,000 and 160,000 g / mole, and most preferably between 80,000 and 140,000 g / mole. The molecular weight of PMMA measured by the following measurement method (internal analysis direction No. LCO12 of EMS CHEMIE AG) is: The distribution of the molecular weight and weight average molar mass (Mw) of PMMA is determined by gel dialysis chromatography (GPC). That is, a GPC measurement device having a basic component pump device for liquid chromatography, a chromatography column, and a detector. This measurement method was performed using a Waters Co. type GPC 150A device with an IR detector. A 250 mm x 7 mm (diameter) fourth independent tubing string is connected to one of a series of lengths forming the lm header string. These columns are packed with 10 μπι MERCK LiChrogel® and combined with PS4000, PS400, PS20 and PS4 (referred to as pore size) to fill four separate sections so that each fraction of PMMA molecular weight can be selectively separated . Chloroform was used as a storage solution for PMMA samples and 0.1% 1,2-dichlorobenzene was used as a buoy. Chloroform with a flow rate of 1 ml / min was used as the eluent. In order to make 10 (please read the note on the back to write this page first); Thread-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 490513 A7 5280pif.d〇c / 〇〇8 ηγ 5. Description of the invention (2) Prepare samples, place each 50mg PMMA sample in a 20mL sealed glass container, then fill it with a labeled storage solution, and stir until completely dissolved. First, at least 5 standard units of PMMA need to be prepared in the same way, which uses POLYMER LABORATORIES Co. to measure the molecular weight, and this molecular weight range is 5,720 < MW < 360,000. The measurement of molecular weight is calculated using the standard tritium. Each glass container was injected with 200 µl of sample solution. All processing is performed below. According to the narrow standard of this method, the measurement of tritium (gel dialysis chromatography) is made using GPC software, MILLENIUM (by WATERS). The amount of PMMA mixed is in the range of 0.1-4% relative to the polyester as the fiber-forming polymer. The preferred range is between 0.2 and 3%, and most preferably between 0.3 and 2%. Polymethyl methacrylate as a PET additive can be mixed using, for example, a so-called continuous modification polymer melt (DE 40 39 857 C2) melt conditioning method. The contents of DE 40 39 857 C2 are hereby incorporated by reference. The amount of partial melting that is polymerized by condensation or remelted is separated from the main molten main stream. This part of the tributary enters the side stream extruder, and is then mixed in the form of granules and powders, preferably in the form of pearls, and then dispersed. The dispersed and mixed molten concentrate is returned directly to the main melting line and then diluted to the final concentration. In addition to the above-mentioned melt processing method, for example, it can be injected into a main melt stream by a melt extruder to produce a pure amount of added melt. Then, in the fiber-forming dielectric polymer (such as polyethylene terephthalate, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 cm)) ------------ --Install—— (Please read the note on the back first to write this page) -line- 490513 A7 5280pif.doc / 008 07 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (5. Description of invention (q) ester) A homogeneous and additive inclusion body provides a relatively aligned mix of ingredients. If PET pellets are used as the starting material and melted in the spinning extruder, you can directly measure the additives (in the form of granules, powders or pearls) used as PET pellets in the spinning extruder. Form) of PMMA. The additives were dispersed in polyethylene terephthalate, and then the molten mixture was spun. Since the melt treatment method facilitates the fine distribution of the amount of molten PET, the pearly PMMA starting form is preferred among the various forms mixed here. In addition, commercial PMMA products are usually easier to obtain in this form. This pearly form is conceivable as a sphere with a diameter of about 0.3 mm, sometimes called a grit. Additives can be used both as a pure matrix and as the main mix. In addition, the remaining added substrates or additives can be shredded and spun at the same time. The polyethylene terephthalate itself contains general additives such as a delustering agent (titanium dioxide), a stabilizer, and a catalyst. The polyethylene terephthalate (PET) or polyester in this application is a polyester containing at least 80% polyethylene terephthalate units, and the largest 20% units, such as diethylene glycol, 1,4-butanediol, or dicarboxylic acids other than terephthalic acid, such as isophthalic acid, hexahydroterephthalic acid, and dibenzoic acid. Polyethylene terephthalate can be selectively modified with a small molar amount of a branching agent having 3-4 functional alcohols or acid groups, such as trimethylpropane, trimethyloletane, pentaerythrite, glycerol, trimesic acid, trimellitic acid or pyromellitic acid. However, in order to modify the dyeing ability, the starting polyester can include (please read the precautions on the back first-write this page) • Thread! Φ This paper size is in accordance with China National Standard (CNS) A4 (21〇X 297mm) 490513 5280pif.doc / 〇〇8 A7 B7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Additives, such as sodium-3,5-dicarboxybenzol sulfonate 〇 On the melting line, for example, other dynamic and / or static mixers can be used. Therefore, dynamic and / or static mixers can be placed directly before the spinning assembly. In the embodiment of the present invention, first, a ready-to-use, dispersed molten mixture that can be produced in any of the mixed variants is spun into agglomerates, rather than spun into fibers. High-efficiency agglomerates can be processed by conventional spinning machines with a melt extruder and spun into fibers or filaments. In this process, secondary processing manufacturers, such as customers of pellet manufacturers, use the polyester of the present invention to modify, without the need to provide conventional spinning machines with expensive measuring and mixing equipment, and without the need to purchase additional separate additive. In this way, for secondary processing manufacturers, all processing is as simple as the same PET pellets. Figures 1, 2 and 3 show cross-sectional images of the REM melt-spun cross-section of the dielectric polymer (PET) according to the present invention. This is the wafer surface in the non-forward direction. In particular, Figure 3 (rod-shaped, lateral cross-section) shows the axial inclusions of the PMMA additive (referred to the fiber axis). The invention is illustrated in detail by the following examples, which do not limit the invention. A conventional spinning machine is, for example, a machine described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. AlO, Fibers, 3 General Production Technology, pp. 550-561. Example The results of testing using a six-fiber manufacturing spinning device are shown in Table 1. Table (please read the note on the back first to write this page)-Binding-Threads * This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 490513 5280pif.doc / 008 A7 B7 Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives. 5. The invention is clear (丨 () 1) The results of the spinning test at a take-up speed (Vwick) of 4,950 meters per minute. The spinning temperature range is 208-295 ° C. , Preferably 285QC. The cooled filaments need to be passively cooled, such as DE197 16 394 C1. After the cooling wire spinning step is performed, the yarn ball is guided to a low-temperature godet-duo, and then coiled. The speed of the roller is 5000 m / min, which is the speed at which spinning of each variant except the blank sample "Blank-2" starts. The speed of the roller of the species "Blank-2" (conventional, does not require additives) It is 3225 m / min. The mixed additives are melt-processed (DE 40 39 857 C2), which is usually applied to the melt modification of conventional continuous polyethylene terephthalate condensation polymerization connected to a spinning machine. In order to make yarn balls, we often use EMS- CHEMIE AG polyethylene terephthalate, also known as GRILENE® M764. The additive used is polymethyl methacrylate from DEGUSSA Co., also known as DEGALAN⑧G8E. Its molecular weight (average weight) is 126,580 g / mol. The concentration is 0.65- (K90wt%. The average lateral diameter of the polymethyl methacrylate inclusions is less than 400nm (see Figures 1, 2, and 3). The spinning behavior is good. Only the entire silk cake is manufactured (Spool). Table 2 shows the textile information of the textured yarn. The quality information achieved by the modified polyester is consistent with good, conventionally manufactured yarns. However, when there is only general The POY yarn is spun at a spinning speed of about 3200 m / min, and the productivity distribution of its spinning machine is very large. (Please read the note on the back first. Matters »Write this page)
I ί 言 Τ ί 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 490513 五、發明說明（（1) A7 5280pif.doc/008 R7 表格I : 6種纖 維夕製浩 配置 添加物型 熊 G8E G8E G8E Blank-1 Blank-2 量％ 0.65 0.76 0.90 RD% 120.6 126.6 134.1 64.7 121.8 RF(Cn/dt ex) 2.4 2.24 2.01 3.07 2.31 滴定量 (dtex) 129.7 131.2 129.7 124.9 125.3 Vwick(m/ min)=捲 取涑度 4950 4950 4950 4950 3170 系方絲行爲 優 優 優 佳 優 直禅（nm) 小於400 小於400 在噴絲頭 處的平均 測向”棒 狀直徑” (請先閱讀背面之注意事項寫本頁) 裝I ί 言 Τ ί The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 490513 V. Description of the invention ((1) A7 5280pif.doc / 008 R7 Form I: 6 types of fibers Additive type Bear G8E G8E G8E Blank-1 Blank-2 Volume% 0.65 0.76 0.90 RD% 120.6 126.6 134.1 64.7 121.8 RF (Cn / dt ex) 2.4 2.24 2.01 3.07 2.31 Titration (dtex) 129.7 131.2 129.7 124.9 125.3 Vwick (m / min) = degree of coiling 4950 4950 4950 4950 3170 The square wire behaves excellent excellent good good straight zen (nm) less than 400 less than 400 average direction-finding "rod-like diameter" at the spinneret (please read the note on the back first) Matters written on this page)
-丨線I 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 5280pif.doc/008 B7 添加物型熊 G8E G8E Blank-2 量％ 0.65 0.76 RD 21.3 21.7 21.4 RFiCn/dtex) 4.08 4.06 4.1 滴宙量（dtex) 80.7 77.1 75.8 Vtex(m/min)= 拉伸締鬈製程 的捲取涑彦 800 800 800 垃伸比銮 1.68 1.74 1695 紡絲行爲 優 優 優 490513-丨 Line I Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. The paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) A7 5280pif.doc / 008 B7 Additive type bear G8E G8E Blank-2 Quantity % 0.65 0.76 RD 21.3 21.7 21.4 RFiCn / dtex) 4.08 4.06 4.1 Drop volume (dtex) 80.7 77.1 75.8 Vtex (m / min) = coiling during the stretching process 涑 彦 800 800 800 waste stretch ratio 1.68 1.74 1695 Spinning behavior Youyou 490513
五、發明說明（C (請先閱讀背面之注意· 事項me寫 本頁) 裝 訂· 表格I與表格II之省略的部分之意義爲： G8E=以特定量添加至PET之DEGUSSA Co. PMMA型態 的添加劑，其商品名稱爲DEGALAN®。V. Description of the invention (C (please read the notes on the back and the items on this page first) Binding · The meaning of the omitted part of Form I and Form II is: G8E = DEGUSSA Co. PMMA type added to PET in a specific amount Additive, trade name DEGALAN®.
Blank-1=沒有添加添加劑之空白變體（比較之例子），僅具 有 PET 型態 Grilene® M764 的 EMS-CHEMIE AG(其每測 量l%m-cresol之相對黏度爲1.64)。 經濟部智慧財產局員工消費合作社印製Blank-1 = A blank variant with no additives (comparative example), only EMS-CHEMIE AG with PET type Grilene® M764 (the relative viscosity per measured l% m-cresol is 1.64). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
Blank-2=類似Blank-Ι，但具有較低的紡絲與捲取速度。 RD=斷裂延長量 RF=斷裂處的張力 雖然本發明之較佳實施例與其特徵均揭露如上，但 任何熟習此技藝者，在不脫離本發明之精神和範圍內，當 可更動、替代與潤飾本發明所揭露的聚合混合物及其纖維 16 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 490513 A7 5 2 8 0pif . d〇c/Q〇8 _By___ 五、發明說明（M ) 的製造方法，因此，本發明之範圍並不限於上面所描述， 其保護範圍當視後附之申請專利範圍所界定者爲準。 --------------裝--- (請先閱讀背面之注意事項HI寫本頁) 訂· •線· 經濟部智慧財產局員工消費合作社印製 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Blank-2 = Similar to Blank-1, but with lower spinning and winding speeds. RD = elongation at break RF = tension at the break Although the preferred embodiment of the present invention and its characteristics are disclosed as above, anyone skilled in the art can change, substitute and retouch without departing from the spirit and scope of the present invention. The polymer mixture and its fibers disclosed in the present invention 16 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 490513 A7 5 2 8 0 pif. Doc / Q〇8 _By___ 5. Description of the invention ( M). Therefore, the scope of the present invention is not limited to the above description, and its protection scope shall be determined by the scope of the attached patent application. -------------- Install --- (Please read the note on the back HI to write this page) Order · • Line · Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 7 paper sizes Applicable to China National Standard (CNS) A4 (210 X 297 mm)